多孔羟基磷灰石生物陶瓷的进展

多孔羟基磷灰石生物陶瓷是一种性能优异的人体硬组织修复材料，在植入界面后它具生物降解性，置入体内能逐步参与代谢以至最终与人体骨结合成一体。本文在综合大量国内外文献的基础上，阐述了多孔羟基磷灰石生物陶瓷的性质、研究和发展。     

Modification of the porosity of pillared clays by carbon deposition. I. Polymer carbonization

In order to use pillared clays (PILC) for selective adsorption, further modifications of the porous structure are necessary. The deposition of carbon residues onto the porous structure of pillared clays by the carbonization of polymers (polyvinylalcohol) was proposed to achieve a controlled modification of the pore size. Ti and Al-pillared clays (calcined and non-calcined) were impregnated with PVA (different grades and different concentrations and subsequently carbonized to form carbon phases. The effect of the carbon deposits on the porosity of Ti- and Al-PILC is discussed in terms of pore-blocking, pore-filling and pore-narrowing. The deposition of carbon using PVA resulted in a complete pore-blocking for Al-PILC and in a narrowing of the pore size distribution for Ti-PILC, without achieving a controlled pore-narrowing.     

沼蛤侵蚀对混凝土的性能损伤试验研究

沼蛤侵蚀给混凝土带来的性能影响对防治措施的选择与决策具有重要的参考意义。对于受侵蚀1年的自制试件和受侵蚀20余年的现场芯样,本文采用浸泡增重法、压汞法、场发射环境扫描电镜法和热重法分别测试了有贝附着组和无贝对照组的表层吸水率、表层孔隙特征与孔径分布、表层形貌和成分变化,以及表层钙成分含量变化这4个指标,研究了沼蛤侵蚀混凝土前后以及侵蚀时间对微观性能的影响。定量分析表明:沼蛤附着侵蚀混凝土后,混凝土不同尺寸的孔隙均有增加,同时表观密度分别下降了13.5%(侵蚀1年)和19.5%(侵蚀20余年),表层吸水率分别增加了82%(侵蚀1年)和101%(侵蚀20余年),混凝土表面的铝元素、铁元素和锰元素大幅增加,钙元素尤其是碳酸钙流失严重,分别减少了41.7%(侵蚀1年)和82%(侵蚀20余年)。因此,沼蛤的侵蚀会造成混凝土的微观性能损伤,受侵蚀时间越长,性能损伤越严重。     

孔隙液体对透明土渗透特性影响对比试验

针对熔融石英砂与混合油、溴化钙及蔗糖等孔隙液体制配成的3种透明土试样,开展渗流液体与孔隙液体一致或者不一致两种情况下的常水头渗透试验,测得透明土材料在不同孔隙液体、粒径及相对密实度等情况下的渗透率,以及水在3种透明土试样中的渗透过程;并与福建标准砂相关试验结果进行了对比分析。进而开展透明土试样电渗可视化模型试验,初步探讨孔隙液体、渗透率等因素对电渗过程与机理的影响规律。试验结果表明,透明土试样渗透特性不仅与粒径分布、相对密实度等因素相关,而且与孔隙液体种类相关;混合油、溴化钙溶液制配成的透明土渗透率与天然砂土渗透率最为相近。     

Preparation of microporous chlorinated poly(vinyl chloride) membrane in fabric and the characterization of their pore sizes and pore‐size distributions

Chlorinated poly(vinyl chloride) (CPVC)/poly(vinyl pyrrolidone) (PVP) membranes were prepared by using the solvent system tetrahydrofuran (THF)/n‐butyl alcohol (n‐BA) to investigate the possibility of pore size and pore‐size distribution control. The coagulation of CPVC/PVP solution was induced by the exposure to water vapor at 25 (±0.5)°C. The average pore diameter, d_p, and the size distribution of pores on the surface of the membrane were quantified through the image analyzer from the images visualized by field emission scanning electron microscope (FE‐SEM). Surface pore size and distribution of the prepared CPVC/PVP membrane were strongly affected by the relative humidity (RH) in the environment and the content of PVP used as an additive. Particularly, in the case of CPVC membrane without PVP, the mean pore size was 0.15–0.2 μm, depending on the RH. The pore distribution became broad with the increase of the RH. The membranes had open pores as confirmed by the hydraulic permeation experiment. In addition, the water flux and membrane resistance (R_m) were greatly affected by the composition of polymer solution and the RH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1195–1202, 2002     

基于微观孔隙通道的饱和/非饱和土渗透系数模型及其应用

从微观角度揭示土体变形对饱和/非饱和渗透系数的影响机理,建立相应的预测方法,对于饱和/非饱和土的渗流分析及水力耦合研究具有重要的科学意义。利用流体力学理论,建立了微观孔隙通道渗透系数与等效孔径的关系,在此基础之上,结合毛细理论建立了饱和/非饱和渗透系数与土-水特征曲线的关系模型,并利用已有试验数据验证了模型的合理性。结合该模型与变形条件下土-水特征曲线预测方法,对变形条件下武汉黏性土饱和/非饱和渗透系数进行预测,结果表明黏性土在压缩变形条件下:饱和渗透系数呈数量级的减小,预测值与实测值均吻合较好;双对数坐标下,非饱和相对渗透系数在进气值之后随基质吸力增加而减小,不同初始孔隙比条件下其斜率近似不变,整体呈现"毛刷型"分布,相同基质吸力条件下,初始孔隙比越小,相对渗透系数越大;非饱和渗透系数,进气值之前近似为饱和渗透系数,进气值之后随基质吸力增大而减小,不同初始孔隙比的变化线近似重合。     

Permeability characteristics of carbonated concrete considering capillary pore structure

During carbonation process, the calcium phases present in cement are attacked by CO₂ and converted into CaCO₃ and the permeability of concrete is changing due to the change in porosity. The rate of carbonation depends upon porosity and moisture content of the concrete. Especially in underground reinforced concrete structures, the interior portion of concrete surface may be exposed to carbonation and the exterior portion of concrete surface exposed to wet soil or underground water. As carbonation proceeds from outer surface into internal portion of concrete, microstructure is also changed continuously from outer surface into internal portion of concrete. Even the deteriorations in the structures due to the carbonation have been reported more, research on permeability characteristics of concrete considering carbonation and micro-structural information is very scarce.In this study, the permeability coefficient in carbonated concrete is derived by applying a capillary pore structure formation model in carbonated cement mortar and assuming that aggregates do not affect carbonation process in early-aged concrete as a function of porosity. The permeability obtained from the micro-level modeling for carbonated concrete is verified with the results of accelerated carbonation test and water penetration test in cement mortar.     

直接甲醇燃料电池用碳气凝胶载铂催化剂的研究

利用溶胶—疑胶方法制备了高比表面积的碳气凝胶,利用浸渍还原法制备了Pt/碳气凝胶和Pt/C催化剂。采用BJH和TEM考察碳气凝胶的孔径分布和金属粒子的大小与分布,循环伏安曲线测试考察Pt/碳气凝胶对甲醇催化氧化性能的影响。结果表明,碳气凝胶的比表面积达到480 m2/g,孔径分布良好,催化剂金属颗粒较小,分散较好,循环伏安曲线图显示出Pt/碳气凝胶比传统的Pt/C对甲醇催化氧化性能高。     

Silica Nanoboxes as New Nano-structured Materials: Their Secondary Synthesis from Alumina-Rich Zeolites

Novel silica nanoboxes were prepared by controlled dealumination of Na-X and Ca-A type zeolites using ammonium hexafluorosilicate (AHFS). The silica-richer the parent zeolite, the smaller the average pore size produced and the narrower the pore size distribution obtained. This was due to the specific reactivity of the extracting agent with the zeolite framework aluminum atoms. High temperature calcination of the dealuminated X-zeolite (ammonium form) resulted in mesoporous materials exhibiting an ink-bottle shape, a quite high surface area (330 m²/g, no micropores), an average pore diameter of 4.5 nm with a quite narrow pore size distribution (± 1.0 nm) and finally, a pore opening diameter of 3.9 nm. The latter was determined by using the nitrogen sorption isotherms (BET technique) and related pore volume data. The sorption behavior also suggested the interconnecting character of the newly created nanoboxes. The periodicity of these nanoboxes throughout the mesoporous material was clearly shown by X-ray powder diffraction at very small angles. These materials, herein called monomodal nanoboxes because of the absence of micropores in the structure, were also thermally stable. Incorporation of orthosilicate into the obtained silica nanoboxes, in accordance with the recently developed technique for pore size engineering in zeolites, led to materials with smaller pore openings but having almost the same textural properties. Solid superacidic materials were prepared by incorporating a liquid superacid (triflic acid or trifluoromethanesulfonic acid) into the silica nanoboxes using the wet impregnation technique. The maximum triflic acid loading which did not significantly affect the mesoporous framework of the materials was 24 wt%. As a reference, the maximum loading of less acidic sulfuric acid was slightly lower. All this showed the high chemical stability of the silica nanoboxes for supporting very acidic species. Temperature-programmed desorption using a combined DTA/TGA system allowed the identification of the bound phases and some liquid phase of the loaded triflic acid.     

Exploration of mesoporous structure of tunisian raw and acid-leached phosphate ore particles

Rock phosphate fractions were examined for their porous structure by nitrogen adsorption. The pore size distribution and the shape of pores does not seem to depend on the particle size. The specific surface area values present two regions, one above and one below that of the particles with 125 μrn diameter. Particles of a given size were leached with dilute phosphoric acid (1.5 mass% P₂O₅) at 25°C. It was observed that there is a widening of the initial pores during leaching. The particles collected at the initial period of the reaction are pitted and those collected at the final period are disintegrated.